Review
Chemistry, Physical
Tong-De Tan, Ze-Shu Wang, Peng-Cheng Qian, Long-Wu Ye
Summary: Ynamides, as electron-rich heteroatom-substituted alkynes, have proven to be versatile reagents for organic synthesis and have received extensive attention. Radical reactions of ynamides, categorized by radical attack at the alpha-position and beta-position, are reviewed in this article to highlight reaction selectivity, scope, mechanism, and applicability. The aim is to provide a comprehensive summarization of these advances to guide the further development of ynamide chemistry.
Article
Chemistry, Multidisciplinary
Mithilesh Kumar Nayak, Pallavi Sarkar, Benedict J. Elvers, Sakshi Mehta, Fangyuan Zhang, Nicolas Chrysochos, Ivo Krummenacher, Thangavel Vijayakanth, Ramakirushnan Suriya Narayanan, Ramapada Dolai, Biswarup Roy, Vishal Malik, Hemant Rawat, Abhishake Mondal, Ramamoorthy Boomishankar, Swapan K. Pati, Holger Braunschweig, Carola Schulzke, Prince Ravat, Anukul Jana
Summary: In this study, a thermally stable dicationic diradical compound was synthesized and confirmed by EPR spectroscopy. The presence of the trans-1,4-cyclohexylene bridge was found to be essential for the successful isolation of this compound.
Article
Chemistry, Organic
Maxime Jarret, Hussein Abou-Hamdan, Cyrille Kouklovsky, Erwan Poupon, Laurent Evanno, Guillaume Vincent
Summary: Divergent oxidative couplings were developed between the indole nucleus and the C16-malonate, leading selectively to the formation of the N1-C16 bond of pleiocarpamine or the C7-C16 bond of strictamine. This approach allowed for the synthesis of the scaffold of talbotine.
Article
Chemistry, Physical
Zhengyi Zhang, Jianqiang Feng, Chao Yang, Haiyang Cui, Wesley Harrison, Dongping Zhong, Binju Wang, Huimin Zhao
Summary: Since the discovery of the Hofmann-Loffler-Freytag reaction over 130 years ago, the study of nitrogen-centred radicals has been widespread. However, catalytic enantioselective intermolecular radical hydroamination remains challenging due to side reactions, short lifetimes of nitrogen-centred radicals, and limited understanding of catalytic steps. In this study, a pure biocatalytic system is repurposed for the photoenzymatic production of nitrogen-centred radicals and enantioselective intermolecular radical hydroaminations. These reactions occur efficiently at room temperature without external photocatalysts and exhibit excellent enantioselectivities.
Article
Chemistry, Multidisciplinary
Doris Chen, Elizabeth Jones, Corey W. Williams, Tan-Khang N. Huynh, Tristan C. McPhail, Stefan France
Summary: In this study, a SnCl4-catalyzed intramolecular, interrupted homo-Nazarov cascade biscyclization method was developed to access angular (hetero)aryl-fused polycycles. The cyclopropyl homo-Nazarov cyclization precursors were formed using a scalable and modular synthetic route, enabling the synthesis of various angular polycyclic products. The method was successfully applied in the total synthesis of (+/-)-1-oxoferruginol, an antibacterial aromatic abietane diterpenoid.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Wenbang Yang, Wenqing Wang, Leran Zhang, Li Zhang, Huapeng Ruan, Zhongtao Feng, Yong Fang, Xinping Wang
Summary: This study provides evidence of 2c-3e sigma-bonds constructed between main-group heteronuclears, as well as rare examples of radical cations involving three-electron sigma-bonds between S/Se and P/As atoms.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Alisa S. Sunagatullina, Ferdinand H. Lutter, Paul Knochel
Summary: In this study, various dialkylmagnesiums were synthesized by reacting primary or secondary alkyl iodides with sBu(2)Mg, and these reagents underwent diverse reactions with different compounds to yield stereodefined products. Mechanistic studies revealed that these reactions proceed via a radical pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Zijian Zhong, Pan Xu, Jinfeng Ma, Aihua Zhou
Summary: A green electrochemical oxidative cross-coupling protocol has been developed for the generation of thiosulfonates and sulfonate esters using sodium arenesulfinates and thiophenols/phenols. The reactions utilize inorganic and non-toxic NaI as redox catalyst and supporting electrolyte at room temperature without the need for oxidant and base, providing good yields of products and tolerating broad substrate scope. Mechanistic studies revealed that the reactions proceed via a radical pathway for the formation of SO2-S and SO2-O bonds.
Article
Chemistry, Multidisciplinary
Darius Vrubliauskas, Benjamin M. Gross, Christopher D. Vanderwal
Summary: In this article, the tolerance of Co-catalyzed MHAT-initiated radical bicyclizations towards oxidation at virtually every position in the substrate, oftentimes in unprotected form, is demonstrated. The functional groups in the substrate can also contribute to high levels of stereochemical control in these complexity-generating transformations. Furthermore, the utility of these reactions in the synthesis of three aromatic abietane diterpenoids is documented.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Shaobin Su, Chengcheng Lin, Hongbin Zhai
Summary: In this study, the total syntheses of (-)-daphnezomines A and B and (+)-dapholdhamine B have been successfully achieved in 16-20 steps through rapid construction of a common core intermediate. Key steps include the synthesis of the azabicyclo[3.3.1]nonane ring system, installation of the bridgehead all-carbon quaternary stereocenter, construction of the aza-adamantane backbone, and assembly of the (+)-dapholdhamine B backbone through 6-endo-trig aminocyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Abdirisak Ahmed Isse, Armando Gennaro
Summary: ATRP, the most powerful technology in Controlled Radical Polymerization, has been greatly enhanced by the introduction of electrochemistry in the past decade, contributing to a better understanding of activation mechanisms, determination of thermodynamic parameters, and electrochemically-mediated ATRP among other aspects.
Article
Chemistry, Multidisciplinary
Daniel Duvinage, Farzin Mostaghimi, Mattis Damrath, Julian Spils, Pascal Komorr, Danila S. S. Odintsov, Matvey Fedin, Leonid A. A. Shundrin, Stefan Mebs, Jens Beckmann
Summary: Sterically encumbered bis(m-terphenyl)chalcogenides were synthesized by reacting the chalcogen tetrafluorides with m-terphenyl lithium. The radical cation [(2,6-Mes(2)C(6)H(3))(2)Te][B(C6F5)(4)] was obtained and fully characterized through single-electron oxidation. However, the electrochemical oxidation of the lighter homologs (2,6-Mes(2)C(6)H(3))(2)E (E=S, Se) was irreversible and impaired by rapid decomposition.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Inorganic & Nuclear
Bindusagar Das, Abhishek Makol, Subrata Kundu
Summary: The synthesis and characterization of isolable radicals of main-group elements have been a long-pursued quest. Considerable progress has been made in isolating carbon radicals, but much less is known about radicals involving heavier p-block elements. This review focuses on the synthesis and properties of isolable phosphorus-centered radicals.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Tony Biremond, Margaux Riomet, Philippe Jubault, Thomas Poisson
Summary: Due to their high versatility, borylated and silylated compounds are essential building blocks for organic chemists. In order to move away from the classical hydroboration/hydrosilylation paradigm, chemists have explored more modern and environmentally friendly methods such as photoredox chemistry and electrosynthesis. This account focuses on our group's novel methods for the generation of boryl and silyl radicals to create C-B and C-Si bonds.
Article
Chemistry, Applied
Yunfei Tian, Luping Zheng, Yuting Yang, Jiayi Liu, Zihan Jing, Zejiang Li, Weijun Fu
Summary: An electrochemical oxydifluoroethylation of alkenes using the anodic oxidative generation of MeCF2 radical has been achieved, resulting in the synthesis of diversified difluoroethylated benzoxazines and lactones in yields of 35-87%. The method was also extended to the synthesis of cyclopropyldifluoromethylated benzoxazines. Mechanistic studies revealed that the reaction proceeded via a radical process involving tandem C-CF2R and C-O bond formation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Medicinal
Dan W. Reynolds, John M. Campbell, Byron S. Johnson, Biren K. Joshi, Kevin L. Facchine, Stacey Long, Thomas M. O'Connell, Iris V. Paulus, Scott L. Sides, Eric S. Kraft, Andrew M. Wolters
JOURNAL OF PHARMACEUTICAL SCIENCES
(2017)
Article
Chemistry, Organic
Robert J. Perkins, Hai-Chao Xu, John M. Campbell, Kevin D. Moeller
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2013)
Article
Chemistry, Organic
Hai-Chao Xu, John M. Campbell, Kevin D. Moeller
JOURNAL OF ORGANIC CHEMISTRY
(2014)
Article
Chemistry, Multidisciplinary
John M. Campbell, Hai-Chao Xu, Kevin D. Moeller
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2012)
Article
Spectroscopy
Brian M. Patterson, John Campbell, George J. Havrilla
X-RAY SPECTROMETRY
(2010)
Article
Chemistry, Analytical
John M. Campbell, Kaitie Grinias, Kevin Facchine, Benoit Igne, Jacalyn Clawson, John Peterson, Andy Wolters, Jeremy Barry, Simon Watson, Kevin Leach
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
(2019)
Article
Chemistry, Medicinal
John M. Campbell, Chris Foti, Chloe Wang, Neal Adams, Leonardo R. Allain, Gabriela Araujo, Renan Azevedo, Jucara Ribeiro Franca, Simon R. Hicks, Steven Hostyn, Patrick J. Jansen, Dorina Kotoni, Andreas Kuemmell, Stacey Marden, Gregory Rullo, Ana Claudia O. Santos, Gregory W. Sluggett, Todd Zelesky, Steven W. Baertschi
Summary: Stress testing is a critical part of drug development, providing foundational information on the stability characteristics of pharmaceutical products. For solid dosage form drugs, stress testing studies do not need to include solution phase stress testing to be comprehensive.
JOURNAL OF PHARMACEUTICAL SCIENCES
(2022)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)